Determination of uranium in minerals and rocks

A method is described for the determination of uranium in minerals and rocks by spectrophotometry and fluorimetry. After treatment of the sample with hydrochloric acid, uranium is separated from matrix elements by adsorption on a column of the strongly basic anion-exchange resin Dowex 1 x 8 from an organic solvent system consisting of IBMK, tetrahydrofuran and 12M hydrochloric acid (1:8:1 v v ). Following removal of iron, molybdenum and co-adsorbed elements by washing first with the organic solvent system and then with 6M hydrochloric acid, the uranium is eluted with 1M hydrochloric acid. In the eluate, uranium is determined by means of the spectrophotometric arsenazo III method or fluorimetrically. The suitability of the method for the determination of both trace and larger amounts of uranium was tested by analysing numerous geochemical reference samples with uranium contents in the range 10(-1)-10(4) ppm. In practically all cases very good agreement of results was obtained.     

The determination of uranium and thorium in rocks by neutron activation analysis

A neutron activation method is described for the determination of thorium and uranium in rocks at the microgram and submicrogram levels. Radiochemical separations are carried out using the alpha-active nuclides protactinium-231 and neptunium-237 as tracers. The method is applied to the Standard granite XXX and the standard diabase XXX.     

Leaching of uranium,radium and thorium from vertisol soil by ground water

Shallow land burial is routinely used for the disposal of low-level radioactive waste. Natural processes causing leaching of radionuclides can lead to contamination of surrounding ground water and soil by the radionuclides. The comparative leachability of radionuclides U_(nat), ²²⁶Ra, ²²⁸Ra and Th_(nat) from the soil of a radioactive waste disposal site, by ground water was evaluated. The probability of leaching was obtained in the following order Ra (≈77%) > U (≈40%) > Th (≈20%). Observed ratios (OR) were calculated to correlate leachability of radionuclides to that of major cations Ca²⁺ and Mg²⁺. The leaching of the radionuclides was seen to be dependent on Ca²⁺ and SO₄²⁻ leached from the soil. This study provides sitespecific leachability of radionuclides, that can be used as indicator of the tendency for migration or retention in soil. It can play an important role during an unforeseen accident like breach of containment at the waste disposal site leading to contamination of soil and ground water and causing hazard to public via drinking water route.     

Identification and characterization of resistate minerals containing uranium and thorium

A set of natural matrix Standard Reference Materials were developed by the National Bureau of Standards for analytical methods evaluation. These materials were analyzed using a KF fusion procedure and an acid dissolution procedure. The latter method yielded radioactive concentrations that were 15–20% lower then that of the former. This was thought to be due to a fraction of the sample, “resistates,” that did not dissolve during the dissolution. In this study, HF dissolutions were conducted on NIST natural matrix SRMs, in which ~0.08% of total sample mass remained after dissolution. The acid resistant residual materials were concentrated, then dissolved using a LiBO₂ fusion procedure and were found to contain a considerable fraction of the uranium and thorium.     

Sorption of uranium, radium, and thorium from saline solutions on hydrolyzed wood lignin

Sorption of U, Ra, and Th from multicomponent aqueous salt solutions on hydrolyzed wood lignin is studied. The mechanism of radionuclide sorption from saline solutions is suggested on the basis of the results of sequential extraction.     

Separation of radium,thorium, uranium and plutonium on OSTION anion exchanger in atmospheric precipitation samples

An anion exchanger OSTION AT 0807 of Czechoslovak production was tested for the separation of radium, thorium, uranium and plutonium. According to the results, the separation process is suitable for analysis of atmospheric precipitation samples. Separation efficiency can be increased by the repetition of the procedures.     

Sorption of uranium, radium, and thorium by analcym-containing rock and sorbents based on plant tissue

Capacity of analcym-containing rock, hydrolytic wood lignin, and sorbents based on oat straw to absorb uranium, radium, and thorium from acid and weakly acid solutions of their salts was studied. Possible sorption mechanisms of radionuclides are considered on the basis of data furnished by IR spectroscopy and method of successive extractions.     

Effects of pre-irradiation treatments in neutron activation analysis of rocks for measurements of their lanthanoid,thorium and uranium contents

Determination of the lanthanoids, thorium and uranium in silicate rocks has been investigated by neutron activation analysis (NAA). Seven or eight lanthanoids and thorium and uranium were determined by non-destructive instrumental NAA. The numbers of the lanthanoids determined were increased and errors on the final values were reduced by pre-irradiation treatments, which included a coprecipitation process with aluminium as collector to remove the alkali metals and halogens and a solvent extraction process to eliminate iron. The necessity of scandium removal was indicated.     

Dissolution of resistate minerals containing uranium and thorium: Environmental implications

Summary Minerals in the soil range from those that easily weather to those that are very resistant to the weathering processes. The minerals used in this study are referred to as “resistates” because of their resistance to natural weathering processes.¹ It is also known that there are some resistate minerals that have a tendency to contain uranium and thorium within their crystal structure. These resistates can contain as much as 15-20% of the total uranium and thorium present in the soil.⁹ Do resistates dissolve in acids, particularly in the HF/HNO₃ procedures, if not what can be done to the HF/HNO₃ process to dissolve more of the resistate minerals? How would these acid techniques compare to the fusion method used for mineral dissolution? Could the resistate minerals contain considerable amount of uranium and thorium? These were the questions addressed in this research. The comparative data indicate that the use of H₂SO₄ in the dissolution process resulted in ~25% overall increase in the minerals dissolving therefore resulting in a higher yield of extracted uranium and thorium.     

Rapid analysis technique for strontium,thorium, and uranium in urine samples

The electronic properties of the metal atoms encaged in a fullerence cage were investigated using synchrotron X-ray photoelectron spectroscopy. Systematic variations in photoemission of valence band of Gd@C₈₂, Gd@C₈₂(OH)₁₂, and Gd@C₈₂(OH)₂₂ were observed in Gd 5p levels. The results suggest that the electronic properties of the inner metal atom can be efficiently modulated by surface chemistry of the fullerene cage.     

Ultratrace analysis of uranium and thorium in glass

It is today a most common phenomenon that ultratrace analyses for quality control have to be carried out in industrial laboratories far from optimum conditions and in spite of the lack of best suited equipment. It was against this setting that the development of a method for the photometric determination of uranium- and thorium-traces in glasses with arsenazo III was envisaged. The method basically consists of a digestion with HF/HClO₄/H₃BO₃, an extractive preseparation of interfering Ti- and Zr-traces with TTFA/hexanol/CCl₄, an extractive separation of U- and Th-traces with TTFA/TBP/toluene and a final determination of thorium alone (in the presence of photometrically inactive U(VI)) and the sum of Th+U(IV) with arsenazo III.The concentration of uranium is calculated from the difference of the sum of both traces minus the thorium content. Uranium can be determined with nearly the same sensitivity as thorium after reduction to uranium(IV). The most suitable reducing agent for uranium(VI) to uranium(IV) is a mixture of Na₂S₂O₄/CH₂O. An optimization of the arsenazo III concentration for the determination of thorium and uranium yielded an optimal concentration of 80 mg/L arsenazo III: For the reduction of uranium concentrations of 2 g/L of Na₂S₂O₄ and 3.2 g/L CH₂O proved to be optimal. Interferences of this photometric end determination by titanium, zirconium and scandium were investigated quantitatively. The permissible excess for these elements was found to be so low that a trace-trace separation method proved to be necessary. Separation methods were checked for the separation of the matrix components of the investigated glasses from thorium and uranium. One of these methods was suitable after optimization: thorium and uranium are extracted with TTFA/TBP/toluene from a solution containing hydrochloric acid. Back-extraction is carried out with HCl/KMnO₄. For the separation of titanium- and zirconium-cotraces an extra separation method had to be developed: they are extracted with TTFA/hexanol/CCl₄ before the separation of uranium- and thorium-traces from the matrix. The glasses were digested with HF/HX. Fluoride from the hydrofluoric acid is incompletely removed by evaporation and interferes with the extraction of uranium and thorium due to complex formation. Depending on the digestion variant used 162 to 0.23 mg F^– remain in the residue of the digestion of a 5 g sample. This interference was eliminated by a digestion with HF/HClO₄/H₃BO₃ and masking of residual fluoride with AlCl₃.Abbreviations used Arsenazo III 1,8-Dihydroxynaphthalene-3,6-disulphonic acid-2,7-bis [(azo-2)-phenylarsonic acid] - Arsenazo I 1,8-Dihydroxynaphthalene-3,6-disulphonic acid-2-[(azo-2)-phenylarsonic acid] - BPAP 2- (5-Bromo-2-pyridy] azo)-5-diethylaminophenol - EDTA Ethylenediaminetetraacetic acid - HX Designation for a high boiling mineral acid - FAAS Flame atomic absorption spectrometry - FOD 1,1,1,2,3,3,-Heptafluor-7, dimethyl-4,6-octanedione - GFAAS Graphite furnace atomic absorption spectrometry - ICP-MS Inductively coupled plasma — mass spectrometry - ICP-OES Inductively coupled plasma — optical emission spectrometry - LAS Liquid absorption spectrophotometry (classical photometry) - m(Th) Mass of thorium - NAA Neutron activation analysis - pK_Diss Negative logarithm to the base 10 of the dissociation constant of a complex - TBP Tri-(n-butyl)-phosphate - TOPO Tri(n-octyl)-phosphinoxide - TTFA 1-(2-Thenoyl)-3,3,3-trifluoroacetone     

Ultratrace analysis of uranium and thorium in glass

Three methods of determination for uranium and thorium traces and ultratraces in glass were developed: a simple and powerful ICP-MS method exhibiting limits of determination in the one ng/g-range; a complex method with end-determination by classical photometry and a limit of determination for U and Th of 20 ng/g; and a method with chelate-complex formation for U and Th and subsequent GC-detection with a ⁶³Ni-ECD with limits of determination in the g/g-range. These methods are critically compared and tested for real type samples of special glasses.Abbreviations used AAS Atomic absorption spectrophotometry - ECD Electron capture detector - FOD 1,1,1,2,2,3,3-Heptafluoro-7,7-dimethyl-4,6-octanedion - GC Gas chromatography - HFA 1,1,1,5,5,5-Hexafluoro-2,4-pentanedione - ICP-AES, -MS Inductively coupled plasma-atomic emission spectrometry, metry, -mass spectrometry - LAS Liquid absorption spectrophotometry = classical photometry - NAA Neutron activation analysis - NIST National Institute of Standardization and Technology (Gaithersburg, U.S.A.) - TBP Tri-(n-butyl)-phosphate - TFA 1,1,1-Trifluoro-2,4-pentanedione - TTFA 1-(2-Thenoyl)-3,3,3-trifluoroacetone - XRS X-ray (fluorescence) spectrometry     

Uranium, thorium and potassium contents and radioactive equilibrium states of the uranium and thorium series nuclides in phosphate rocks and phosphate fertilizers

Uranium, thorium and potassium contents and radioactive equilibrium states of the uranium and thorium series nuclides have been studied for 2 phosphate rocks and 7 phosphate fertilizers. Uranium contents were found to be rather high (39-117 ppm) except for phosphate rock from Kola. The uranium series nuclides were found to be in various equilibration states, which can be grouped into following three categories. Almost in the equilibrium state, 238U approximately 230Th greater than 210Pb greater than 226Ra and 238U greater than 230Th greater than 210Pb greater than 226Ra. Thorium contents were found to be, in general, low and appreciable disequilibrium of the thorium series nuclides was not observed except one sample. Potassium contents were also very low (less than 0.3% K2O) except for complex fertilizers. Based on the present data, discussions were made for the radiation exposure due to phosphate fertilizers.     

Combination of neutron activation,atomic absorption spectroscopy and conventional methods in the elemental analysis of silicate rocks

Instrumental neutron activation, atomic absorption spectroscopy and conventional methods of analysis were used on eight different silicate rocks and two minerals. Trace elements and major constituents were determined. It was considered that the methods should be regarded as complementary analytical techniques.     

Determination of uranium and thorium in phosphate rocks by a combined ion-exchange — Spectrophotometric method

Summary Determination of Uranium and Thorium in Phosphate Rocks by a Combined Ion-Exchange — Spectrophotometric Method A selective anion-exchange separation and Spectrophotometric method has been developed for the determination of uranium and thorium in phosphate rocks. About 0.2 g of rock sample is decomposed with nitric acid. Uranium and thorium are adsorbed by anion-exchange on an Amberlite CG 400 (NO₃ ^–) column from the sample solution adjusted to 2.5M in magnesium nitrate and 0.1M in nitric acid. Uranium and thorium are eluted consecutively with 6.6M nitric acid and 0.1M nitric acid, respectively. Uranium and thorium in the respective effluents are determined spectrophotometrically with Arsenazo III. Results are quoted on uranium and thorium in NBS standard phosphate rock and others.     

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil has been developed. Analysis involves total dissolution of the samples to allow equilibration of the natural isotopes with added tracers, followed by radiochemical separation using anion exchange chromatography (BioRad AG 1–X8). Further separation and purification is performed employing solvent extraction techniques. Finally, the U and Th fractions are co-precipitated with lanthanum and cerium fluoride, respectively, and quantified by alpha-particle spectrometry. Overall chemical yields range from 60 to 90%. Under normal operating conditions and present counting set up, the minimum detectable concentration (MDC) is approximately 2 Bq/kg for soil samples. This is based on one gram aliquot of sample, 80% chemical yield, and 1000 minute counting with a detector having about 15% counting efficiency. The procedure has been successfully tested with Standard Reference Materials. Various soil samples were analyzed with high chemical yields and fine quality of alpha-spectra. Decontamination factor studies were performed to determine the extent of the carry over of²¹⁰Po,²²⁵Ac,²²⁶Ra, and²²⁹Th into U fraction and²¹⁰Po,²²⁵Ac,²²⁶Ra, and²³²U into Th fraction.     

Electrodeposition of uranium and thorium

Cathodic depositions of uranium and thorium were carried out from a number of baths containing the metal salts, and complexing agents. A reducing agent was also present to prevent oxidation of the element. The deposition was also carried out at controlled pH. The current density ranged from 50 to 200 mA cm^–2. The purity of the deposited metals was better than 99.7%. The mechanism of formation of uranium and thorium is proposed and discussed.     

Haematein as a reagent for thorium, zirconium and uranium

Summary Haematein gives violet colored complexes with thorium and uranium and an orange colored complex with zirconium of the stoichiometric ratios 16, 13, and 11 respectively of the metal and the reagent (Job's method). The reagent and the complexes of thorium, uranium and zirconium show absorption maxima at 520–540 m, 520–540 m 500–520 m respectively. In observations at 540 m in 60 percent aqueous acetone 0.05 mg of thoria (a 12 fold excess of cerite earths has no influence), 0.029 mg U₃O₈ and 0.025 mg of zirconia may be determined. The spectral characteristics of the complexes indicate a similarity in character in spite of differences in stoichiometric composition.